Azo dyes and their production



Patented Sept. 20, 1932 UNITED STATES PATENT OFFICE RAINALD BRIGHTMAN; or IBLACKLEY, MANCHESTER, ENGLAND, ASSIGNOR 'ro IM- PERIAL CHEMICAL INDUSTRIES LIMITED, or WESTMINSTER, ENGLAND .AZO D'YES AND THEIR PRODUCTION N Drawing. Application filed February 12, 1930, Serial No. 427,961, and in Great Britain March 13, 1929.

This invention relates to new trisazo dyes having the following characteristic structure i a wherein R and R represent benzene residues, R represents a coupled residue of an azo dye coupling componentof the class consisting of sulphonie or carboxylic acids of 0 phenols of naphthols or N-substituted naphthylamines or aminonaphthols', and R represents a coupled residue of an azo dye coupling component, and in which the azo groups attached to R are in the meta position to each other and the azo groups attached to R are in the para position to each other, the said trisazo dyes containing at least two carboxylic or sulphonic acid groups. The characteristic structure of these trisazo dyes is shown in somewhat greater detail in the following formula soda wherein R represents a benzene or naphthylamine residue, R represents hydrogen, an alkyl or alkoxy group, R represents hydrogen or an alkyl group, R represents hy-.

drogen, an aryl or acyl group, A represents hydrogen, an amino or substituted ammo resents COOH or SO H group and a: is 1 or 2. These new trisazo dyes have the characteristic property of dyeing regenerated cellulose materials in even level shades. So long as the characteristic structure as set. forth ante is retained these dyestuffs produce even level shades on regenerated cellulose materials and by varying the various substituent groups within the limits indicated above various colors and shades may be produced as desired. This is a new and useful feature of my invention. My invention also comprises processes of dyeing regenerated cellulose materials by applying my new trisazo dyes to the samerand the dyed regenerated cellulose materials thusproduced. Further my'in group, B represents H or OH group, D rep vention also relates to certain processes for producing these new trisazo dyes.

' I find it advantageous to have the residue represented by R comprise a coupled residue of an aminonaphthol sulphonic acid. The residue R may be advantageously either a coupled residue of carboXy phenols or naph' thylamine sulphonic acids, or naphtholsulphonic acids of aminonaphthol sulphonic acids. A large number of desired shades may be produced on regenerated cellulose materials by using dyes having the substituent groups and radicals varied as indicated above.

Certain trisazo dyes derived from 4:4- diaminoazo benzene have been described as substantive dyes for the dyeing of cotton (compare for example German Patents 40,- 740, 72,391 and 72,392) butsuch dyes do not have the valuable property of giving even dyeings on viscose rayon, that is a regenerated cellulose rayon, which I have found to be characteristic of my trisazo dyes as set V forth ante. The trisazo dyes derived from 4:t-diaminoazo benzene are diiferent from my new trisazo dyes in that they have a different structure. My dyes may be considered to be derived from 3 V-diaminoazo benzene and this in part accounts for the difference in structure between my new trisazo gyes and the above mentioned prior trisazo yes.

My new trisazo dyes may be made in various ways. They may be made by tetrazotizing a 3; 4-diaminoazo benzene or a substitution product thereof and coupling with suitable coupling component as herein indicated. Or a diazotized meta-nitro-amine of the benzene series may be coupled with an amine of the benzene series which couples in the para position to the amino group, the 3-nitro-4J- aminoazo benzene thus obtained is diazotized and coupled with one of the specified coupling components and then the resultinginitro disazo dyestuflf reduced to convert the nitro group into an amino group, rediazotized and coupled with a second coupling component.

From the above method it is easily seen that it is not a necessary part of this invention to isolate the 3 4J-diamino azo benzene. Either wherein R represents a benzene or naphthalene residue, A represents hydrogen an amino or substituted amino group, B represents hydrogen or an OH group, D represents a COOH or SO H group, R represents H, CH or OCH R represents H or CH and R represents the coupled residue of an aminonaphthol sulphonic acid.

wherein R represents a naphthalene residue.

wherein A represents H, or van ammo group and R represents a naphthalene residue.

OCHg

9 CH R5 R4.N=N a OCH: 5

' R4-N=N it;

My invention is illustrated but not limited by the following examples, in which the parts are by weight.

Example 1.138 parts of meta-nitroaniline are diazotized in the known manner with 69 parts of sodium nitrite and 250 parts of 36 per cent hydrochloric acid and the diazo-solution is added to a solution containing 187 parts of 21.11lllI16-w-SUIPI1011IC acid and 136 parts of sodium acetate crystals. The mixture is stirred until coupling is complete when it is heated up and the sulphonic group is hydrolyzed by adding an excess of sodium hydroxide solution and stirring a short time. The mixture is then made neutral and after addition of common salt the 3-nitro-F-aminoazobenzene is, filtered 0E, and is diazotized with 69 parts of sodium nitrite and 300 parts of 36 per cent hydrochloric acid. The suspension of diazo compound is run into a solution containing 160 parts of sodium salicylate and 400 parts of sodium carbonate. The coupling is maintained alkaline and stirred until combinationis complete when it is heated up and about 360 parts of sodium sulphide crystals are added. Stirring is coninue until reduction is complete when the resultant aminodisazo dyestuff is salted out and filtered ofi. It is then stirred into water and diazotized by the addition of 69 parts of sodium nitrite and 300 parts of 36 per cent hydrochloric acid. The diazo suspension is then stirred into a well cooled solution containing 239 parts of 2-amin0-8- naphthol-6-sulphonic acid and 400 parts of solution' carbonate. The mixture is 1 maintained alkaline and stirred until coupling is complete when itis heated up and the dyestuif isolated by the addition of common salt. It dyes viscose rayon a reddish-brown shade; This trisazo dye in the form of the freeacid may be representedby the following formula If in place of 239 parts of 2-amino-8naphthol-6-sulphonic acid in the above example there are used 315 parts of 2-phenylamino- 5-naphthol-7-sulphonic acid, the dyestuif obtained dyes viscose rayon a red shade. This trisazo dye in the form of the free acid may be represented by the following formula Similarly by the use of 2 16 parts of sodium 1-naphthol-5-sulphonate in place of 160 parts of sodium sodium salioylate and 315 parts of 2-phenylamino-8naphthol6-sulphonic acid in place of 2amino-8-naphtho1-6- sulphonic acid I obtain a dyestuff giving brown dyeings on viscose rayon. This trisazo dye in the form of the free acid may be represented by the following formula:

.Ewample 3-138 parts ofm-nitroaniline are diazotized in the known manner and the diazo solution is added to a solution of 137 COOH naphthol-G-sulphohic acid and 400 parts of sodium carbonate. Stirring is continued untilcoupling is complete, when the mixture is heated up and 360 parts of sodium sulphide crystals are added. After stirring to complete the reduction the amino-disazo dyestuff is salted out by the addition of common salt GOOH and filtered. It is then diazotized with 69 parts of sodium nitrite and 300 parts of hydrochloric acid and the diazo suspension is stirred into a cold solution containing 319 parts of 1:8-aminonaphthol-2:l-disulphon- 9 io acid. The coupling is maintained alkaline and stirred until combination is co1nplete when it is heated up andthe dyestulf isolated by the addition of common salt. It

forms a dark powder dyeing viscose rayon a blue shade. This dye has the following formula OCHa HOQS

parts of in-amino-p-cresol methyl ether in 100 parts of 36 per cent hydrochloric acid. 136 parts of sodium acetate crystals are added and the mixture is stirred until coupling is complete when the nitroaminoazo dyestuif is filtered off and diazotized with 69 parts of sodium nitrite and 300 parts of hydrochloric acid. The diazo suspension is stirred into a solution of 2 16 parts of the sodium salt of 2- addition of common salt.

OCH;

Hal

Example 3. .169 parts of L-nitro-Q-anisidine are diazotized in the known manner with 69 parts-of sodium nitrite and 300 parts of 36 per cent hydrochloric acid and to the diazo solution there is added a solution containing 187 parts of aniline-w-sulphonic acid, 136 parts of sodium acetate crystals are added and after stirring until coupling is complete the dyestuif is converted by hydrolysis into the nitroaminoazo dyestuff as described in Example 1. The resultant nitroaminoazo dyestuff is filtered-off and diazotized with 69 parts of sodium nitrite and 300 partsof 36 per cent hydrochloric acid. The diazosuspension is stirred into a solution containing 152 parts of o-cresotinic acid and 400 parts of sodium carbonate. The coupling is maintained alkaline and stirred until combination is complete, when it is heated up and the dye-stuff reduced by the addition of 360 parts of sodium sulphide crystals. l/Vhen reduction is'complete the aminodisazo dyestufl' issalted out, filtered off and .diazotized with 300 parts of 36 per cent hydrochloric acid and 69 parts of sodium nitrite. The diazo suspension is stirred into a cold solution of 337 parts of sodium 2-phenylamino-8-naphthol-6-sulphonic acid and 400 parts of sodium carbon ate. The mixture is maintained alkaline and stirred until coupling is complete when it is heated up and the dyestuff isolated by the It dye-s viscose rayon a yellowish brown shade. This trisazodye in the form of the free acid may be represented the following formula con;

; V y H3 OOH A similar dyestufi is obtained if the l-nitro- 2-anisidine of the above example is replaced by 152 parts of 4nitro-2-toluidine. This similar dyestufl in the form of the free acid may be represented by the following formula Example 4.138 parts of m-nitroaniline are diazotized in the usual manner and to the diazo solution there is added a solution containing 107 parts of o-to-luidine. 136 parts of sodium acetate crystals are added and stirring is continued until coupling is complete, when the 3-nitro-4-amino-3-methylazobenzene is filtered off. The nitroaminoazo dyestuff is diazotized and coupled with 138 parts of salicylic acid (according to the procedure indicated in Example 1). The nitro disazo dyestufi" is reduced with sodium sulphide and the resultant aminodisazo dyestuff Example 5 .242 parts of 3: 4-diamino-5- methoxy 2 methylazobenzene are tetrazotized with 300 parts of concentrated hydrochloric acid and 138 parts of sodium nitrite.

The suspension of tetrazo compound is stirred into a well cooled solution containing 262 parts of sodium 2-amino-8-naphthol-6-sulphonate and about 600 parts of sodium carbonate. After stirring a short time there is added a solution containing 237 parts coon of Q-methylamino-naphthalene-7-sulph0nic acid. The coupling is stirred until combinationis complete, when it is heated up and the dyestuff precipitated With common salt. It dyes VlSCOSG rayon in brownish black shades. This trisazo dye in the form of the free acid may be represented by the following formula OCH:

A somewhat similar shade is obtained if in place of the EZ-methyl-aminonaphthalene-7- sulphonic acid there is used 319 parts of 2: 8- amino-naphthol-3 6-disulphonic acid. This second trisazo dyestufi' in the form of the free acid has the following formula 0 OH: I

EmampZe 6.242 parts of 3: 4-diamino-5'- methoxy-2-methylazobenzene are tetrazotized with 300 parts of concentrated hydrochloric acid and 138 parts of sodium nitrite. The suspension of tetrazo compound is stirred into a cold solution of 343 parts of 2-benzoylamino-8-naphthol-6-sulphonic acid, containing about 600 parts of sodium carbonate. After stirring for some time a solution containing 239 parts of 19-amino-5-naphthoh7- sulphonic acid is added and stirring is continued until combination is complete. The dyestufi' is then salted out with common salt. It dyes viscose rayonin violet blue shades. This trisazo dyestufl' in the form of the free acid may be represented by the following formula soan 3: -diamino-5-methoxy 2 methylazobenzene is obtained by coupling m-nitrodiazobenzene with metaaminopara cresolmethyl ether and reducing the 3-nitro-4='-amino-5 methoXy-Q-methylazobenzene (brown, m. p. about 163 C.) with sodium sulphide. It

forms reddish-brown crystals, which, crystallized from toluene melts at 164-55 C. 3: 4.-

diaminoazobenzene forms brownish crystals HN-CH:

Having now particularly described and ascertained the nature of my said invention and in what manner the same is to be performed, I declare that what I claim is 1. In the manufacture of trisazo dyes having the following formula R5 I gangs...

Rs R5 I OCH:

with an azo dye coupling component and an azo group in the 3 position and coupling with a second azo dye couplin'g'component, when X is an amino group the said azo benzene compound being "1 tetrazotized and coupled with two azo dye coupling components and when X is a 'nitro group the said azo benzene compound being diazotized and coupled with an azo coupling component, the disazo compound thus obtained reduced to convert said nitro group into an amino group,

rediazotized and coupled with a second azo' dye coupling component.

2. In the manufacture of trisazo dyes hav- 1 ing the following formula wherein R5 represents a benzene or naphthalene residue, A represents hydrogen, an amino or substituted amino group, B represents hydrogen or OH group, D represents COOI-I or SO H, R represents H, CH or OCH R represents H or CH and R represents a coupled residue of an aminonaphthol sulphonic acid from 3: L-substituted aminoazo benzene compounds having the following structure.

wherein R and R have the same significance as above, the process which comprises tetrazotizing said 3 4-substituted azo-benzene compound and coupling with one molecular proportion of an aminonaphthol sulphonic acid OCH;

NH: 5H3

the process which comprises tetrazotizing said azo benzene compound and adding the tetrazo compound thus obtained to a well cooled sodium carbonate solution containing consisting of 2-amin0-8-naphthol-6-sulphonic acid and 2-benzoyl amino-8-naphthol-G-sulphonic acid, stirring the mixture, then addlng a solution containing an azo dye ing the following formula c'oup'ling c'omponent of the class' consisting of Z-methyl-amino naphthol 7 sulphonic acid, 2 :8-aminona'phthol, 8 6 disulphonic acid and l-amino-5-naphthol-7-sulphonic acid; stirring this mixture until coupling is complete and then isolating the trisazo dye thus produced.

4:. In the manufacture of trisazo dyes having the following formula wherein R representsa benzene or naphthalene residue, A represents hydrogen, an amino or substituted amino group, B represents hydrogen or a hydroxyl group, D represents a GOOH or S0 group, R represents H, CH

'or OCH group, R represents PLCH, group and R represents the coupled residue of an amino-naphthol sulphonic acid, from 3%- substitutedazo benzene compounds having the structure wherein R and R have the same significanoe as above, the process which comprises.

diazotizing the said aminoazo benzene compound,'coupl1ng with an azo dye coupling "component having the following formula wherein B A, B, and D have the same sig- 'nificance asabove, reducing the disazo compound thus produced to convert the Intro group into an ammo group, redlazotizmg and coupling-with an aminonaphthol sulphonic acid, and then isolating the trisazo dye thus obtained.

5. Inithemanufacture of trisazo dyes havwherein R represents hydrogen, CH or V d h h an azo dye coupling component-of the class 90711113011171? @Vmg't e formula N02 Re wherein R and R have the same significance as above, the process which comprises diazotizing said azo benzene compound, coupling with an azo dye coupling component having the following formula GOOH wherein R represents a naphthalene residue, A represents hydrogen, an amino or methyl amino group, R represents H, CH or OCH group, R represents hydrogen or a CH group, R represents a naphthalene residue, R represents hydrogen, benzene nucleus or acylgroup and w is l or 2, from 3:4-azo benzene compounds having the structure Rs I wherein R and R have the same significance as above, the process which comprises diazotlzing said azo benzene compound and coupling w1th an azo dye coupling component having the following structural forwherein A and a: have the same significance as above, reducing the disazo compound thus obtained to convert the nitro group into an amino group, rediazotizing and coupling with an azo dye coupling component having the following structural formula HOH wherein R R and ac have the same significance as above and isolating the trisazo dye thus obtained.

.7. As new products, the trisazo dyes having the probable formula a wherein R and R represent benzene residues, R represents the coupled residue of coupling components of the class consisting of sulphonic acid or carboxylic acid derivatives of a phenol or naphthol or of an N- substitutednaphthylamine or of an aminonaphthol, and R represents the coupled residue of an azo dye coupling component, the azo groups attached to R being in meta position respective to each other and the azo groups attached to R being in para position with respect to each other, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades. V

8. As new products, the trisa-zo dyes having theprobable formula wherein R represents a benzene residue, R represents the coupled residue of a coupling component of the class consisting of sali cylic acid, orthocresotini-c acid, aminonaphthol sulphonic acids and N-substituted aminonaphthalene sulphonic acids, and R represents an aminonaphthol sulphonic acid and R represents H, CH or OCH and in which the azo groups attached to R are in para position with respect to each other, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades.

9. As new products, the trisazo dyes having the following structural formula wherein R represents a coupled residue of the class conslsting of R represents a coupled residue of a coupling component of the class consisting of salicylic acid, orthocresotinic acid, 1-naphtl1ol- 5-sulphonic acid, 2-naphthol-6sulphonic OCH:

acid, 1:4-naphthol-sulphonic acid, l-amino- 5-naphthol-7 -sulphonic acid, 2-amino-8-naphthol-3: G-disulphonic acid, and 2-methylamino-naphthalene-7-sulphonic acid, and R represents a coupled residue of a coupling component of the class consisting of Q-amino- 8-naphthol-'6+sulpho1iic acid, Q-phenylamino- 8-naphthol-6-sulph0nic acid, Q-benzoylamino-8 naphthol-fi-sulphonic acid, EZ-phenyl amino-5-naphthol-7-sulphonic acid, and 1: 8- amino-naphthol-2:4-disulphonic acid, R represents -H, CH or OCH-I said trisazo dyestuffs being capable of dyeing regenerated cellulose in even level shades.

10. As new products, trisazo dyes having the following structural formula wherein R represents a benzene or naphthalene residue, R represents a naphthalene residue, R represents H, CH or OCH R represents H or CH A represents H, an amino or an alkyl substituted amino group, B represents H or OH, D represents OOOH or SO H, R represents H, a benzene nucleus or acyl group and m is 1 or 2.

11. As-new products, trisazo dyes having the following structural formula wherein R represents a benzene or naphthalene residue, A represents H or an amino group, D represents a OOOH or S0 H group and R represents H, a benzene nucleus or acyl group. r v V 12. As new products, trisazo dyes having the following structural formula wherein R represents H, CH or OCH R represents H'or CH and R represents H or a phenyl group. r

13. As new products, trisazo dyes having the following structural formula I a I OOOH AN AMQOH R4-4N=N Ra Ra wherein R represents H, oran alkyl or alkoxygroup, R represents H or an alkyl group and R represents a coupled residue of an aminonaphthol sulphonic acid. t 7

14. As new products, trisazo dyes having the following structural formula f N=NON=N1IMB ($0311 R4N=N Rs wherein R represents a naphthalene residue,

A represents H, an amino or substituted ami- 7 no group, B represents H or OH group, R represents H, OHgvor OCH group, R represents H or OH andR represents a coupled residue of an aminonaphthol sulphonic acid and m is 1 or 2.

15.'As new products, trisazo dyes having the following structural formula wherein R represents a coupled residue of an azo dye coupling component of the class consisting of aminonaphtho'l sulphonic acids COOH and naphthol sulph'onic acids, and R represents H or a phenyl group.

17. As new products, trisazo dyes having the following structural formula r r so H nmmavm a )1 SOaH wherein R represents anaphthalene residue and as is 1 or 2.

18. As new products, trisazo dyes having the following structural formula R1 RI 5, QN=N N=N-RrOH 40.11 Rr-N=N wherein R represents a naphthalene residue, R represents H or CH R represents H or 10 OCH and R represents a coupled residu of an aminonaphthol sulphonic acid.

r 19. As new products, trisazo dyes having the following structural formula HiN 0 H N=N N=N-Rr-OH Am B:

HO N=N wherein R represents a nipthalene residue and R represents H or 0C In testimony whereof I afi'ix m si ature.

RAINALD BRIG T 

